Graphene synthesized by chemical vapor deposition as a hydrogen isotope permeation barrier
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This study investigates the extrusion processes of deuterium and protium using ANSYS-Polyflow. The geometries and computational fluid dynamics (CFD) settings closely replicate the experimental setups and data acquired from the extruder experiments at Oak Ridge National Laboratory (ORNL) for validation purposes. We explore the impacts of (1) slip versus non-slip boundary conditions and (2) the use of constant, temperature-, and shear rate–dependent viscosities, concluding that the implementation of non-slip wall boundary conditions combined with shear rate–dependent viscosity produced more accurate predictions. The simulations achieved excellent agreement with the experimental data, with relative differences of only 5% for deuterium, and 3% to 6% for protium. This is the first time that experimental extrusion data at ORNL have been accurately predicted through high-fidelity CFD modeling. In conclusion, the advancements offer valuable insights and a foundational modeling tool for optimizing pellet injectors for ITER and other future reactor-scale devices.
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Meteorites of the Ornans type 3 carbonaceous chondrites exhibit a range in degree of equilibration, attributed to differing amounts of thermal metamorphism. These differences have been used to split the CO3 chondrites into petrologic sub-types from 3.0, least equilibrated, to 3.7, being most equilibrated. This is similar to the system of assigning the type 3 ordinary chondrites into petrologic sub-types 3.0 to 3.9 based upon thermoluminescence (TL) and other properties; however, the actual range of thermal metamorphism experienced by CO3 chondrites is much less than that of the type 3 ordinary chondrites. The least equilibrated ordinary chondrites show evidence of aqueous alteration and have high D/H ratios possibly due to a deuterium-rich organic carrier. The aim of this study was to determine whether the CO3 chondrites, which have experienced similar secondary conditions to the type 3 ordinary chondrites, also contain a similar deuterium-rich carrier. To date a total of 5 CO3 meteorites, out of a set of 11 for which carbon and nitrogen isotopic data are available, have been analyzed. Ornans has not been analyzed yet, because it does not appear to fit in with the metamorphic sequence exhibited by the other CO3 chondrites; it also has an extremely high delta-D value of +2150 percent, unusual for such a comparatively equilibrated meteorite (type 3.4). Initial results indicate that the more equilibrated CO3's tend to have lower delta-D values, analogous to the higher petrologic type ordinary chondrites. However this is complicated by the effects of terrestrial weathering and the small data-set.
The topics covered include the following: biogenic methane studies; forest soil methane uptake; rice field methane sources; atmospheric measurements; stratospheric samples; Antarctica; California; and Germany.
We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.
The detection of methane in the atmosphere of Mars, combined with evidence showing widespread water-rock interaction during martian history, suggests that the production of methane on Mars may be the result of mineral surface-catalyzed CO2 and or CO reduction during Fisher-Tropsch Type (FTT) reactions. A better understanding of these reaction pathways and corresponding C and H isotope fractionations is critical to deciphering the synthesis of organic compounds produced under abiotic hydrothermal conditions. Described here is a technique for the extraction and analysis of both C and H isotopes from alcohols (C1-C4) and organic acids (C1-C6). This work is meant to provide a "proof of concept" for making meaningful isotope measurements on complex mixtures of solid-phase hydrocarbons and other intermediary products produced during high-temperature and high-pressure synthesis on mineral-catalyzed surfaces. These analyses are conducted entirely "on-line" utilizing a CDS model 5000 Pyroprobe connected to a Thermo Trace GC Ultra that is interfaced with a Thermo MAT 253 isotope ratio mass spectrometer operating in continuous flow mode. Also, this technique is designed to carry a split of the GC-separated product to a DSQ II quadrupole mass spectrometer as a means of making semi-quantitative compositional measurements. Therefore, both chemical and isotopic measurements can be carried out on the same sample.